BIODIESEL PRODUCTION BY

TRANSESTERIFICATION OF WASTE
COOKING OIL USING
HETEROGENEOUS CATALYST
Anirban Pal
Heritage Institute of Technology
Department of Chemical Engineering, 3rd Year
Roll No : 1655034

1
 CONTENTS
• An introduction to biodiesel
• Importance in the current world
• Process of transesterification
• Types of catalyst and a comparative study
• List of catalysts used and their corresponding results
• Insight into the manufacturing proess
• Future prospects
• Conclusion

2
 INTRODUCTION

• Mono-alkyl ester of unsaturated fatty acids

obtained from animal fat and vegetable oil

What is • An alternative and environmentally

friendly source of energy

biodiesel? • Good substituent of fossil fuels

• Notable growing demand in the last few
decades

• First discovered in 1900 that diesel

Methods of engines could run on peanut oil
• Pyrolysis, catalytic cracking, blending and

production micro-emulsification
• Main Sources- Soybean oil, cottonseed oil,

of canola oil, peanut seed oil, palm oil etc

• Major problem- Economic factor

biodiesel • Development

scale production
of transesterification
process and utilisation of WCO for large 3
 IMPORTANCE IN CURRENT WORLD
Reduction of fossil fuels
Ever growing population
sources, increasing of
and their need for
pollution gases emission,
consumption of
and global warming
resources.
effects.

Biodiesel has more

Biodiesel limits biodegradability, lower
greenhouse gas effects combustion emissions
due to the closed CO2 such as CO, SOx, HC, PM
cycle. and lower toxicity than
petro diesel

Can be used in the

Lowered cost of refining,
existing diesel engines
positive economic
with little or no
impact and lessens the
modification. Provides
dependence on oil from 4
better fuel
foreign countries
economy(around 30%)
 TRANSESTERIFICATION
The process of exchanging the alkoxy group of
an ester compound by another alcohol.
Triglyceride lipid fat molecules can be shattered
into four molecules using methanol and caustic
soda as a catalyst

 Transesterification is a catalyzed chemical

reaction between vegetable oils or animal
fats with a low chain alcohol to yield esters
(biodiesel) and glycerine.
 The transesterification process is composed
of three different reversible reactions to
convert triglycerides and alcohol to biodiesel
and glycerine.
 Catalysts used can be both heterogeneous as
well as homogeneous
5
TYPES OF CATALYST USED-PART 1

6
 TYPES OF CATALYST USED-PART 2
 The application of heterogeneous catalysts
in biodiesel production from WCO have
advantages over homogenous catalysts in
terms of
 The higher biodiesel yield; the higher
glycerol purity, easier catalyst separation
and recovery;
 Being cheaper, safer, and more
environmentally friendly and not requiring
a washing step for the crude ester.
 Moreover, these catalysts can eliminate
saponification and hydrolysis reactions. The
heterogeneous catalyst can be divided into
base ,acid and mixed catalyst
 The following chart contains the positives
and negatives of using heterogeneous acid
and base catalysts
7

Solid resin; Calcium ethoxide: zeolite

8
LIST OF CATALYSTS USED AND CORRESPONDING RESULTS
CATALYST TYPE CORRESPONDING WT % OF METHANOL YIELD
REACTION TIME AND CATALYST TO OIL %
TEMPERATURE USED RATIO

Zinc stearate Acid 20 minutes, 473 K 3 18:1 98

Calcined waste Base 2 hours, 338 K 100 ( catalyst 15:1 97.9
coral fragments to oil ratio)
Solid resins Acid 373 K 10 15:1 97.8
Tri potassium Acid 2 hours, 333 K 9 12:1 97.3
phosphate
K-Pumice Base 4 hours, 338 K 5 15:1 96.5
Zinc aluminate Acid 2 hours, 333-473 K 1-10 40:1 95
Zr-SBA-15 Base 12 hours, 433 K 10 30:1 91.7
Calcium Base 5.5 hours, (338+-5) K 3.5 22.5:1 91
ethoxide
 The other heterogeneous base catalysts used are Calcium oxide , Basic solid Mg-Al-CO3 hydrotalcite catalysts in powder form , Barium
meliorated construction site waste marble, Palm ash from empty fruit bunches , Calcium oxide supported on activated carbon , Calcium
ethoxide , Calcium oxide and ZrO2 mixed oxides, etc 9

 The other heterogeneous acid catalysts used are Carbohydrate-derived catalysts from various carbohydrates such as D-glucose, sucrose,
cellulose and starch ,Mg MCM-41, Mg-Al hydrotalcite, and K+ impregnated zirconia ,Amino phosphonic acid resin D418 ,Sulfonating
pyrolyzed rice husk with concentrated sulfuric acid , etc
FACTORS AFFECTING BIODIESEL PRODUCTION
• Increase in temperature increases reaction rate and reduces
reaction time

•Temperature • Beyond optimal level,

• Speeds up saponification reactions
• Facilitates the vaporisation of methanol
• Optimal reaction temperature is 50-60℃

• Initial reaction proceeds slowly

Reaction time • Reaction Rate gradually increases

• Maximum ester conversion attained with increase in reaction time.
• However, beyond optimum time ,yield of biodiesel decreases.

Methanol to • Reversible reaction

• Reaction should be shifted to the right to increase the yield

Oil molar • Highest yield when 100% methanol used in excess

• In transesterification process, ethanol is used due to its renewable,

ratio
easily derivable and eco-friendly nature 10
• 1:6 oil methanol ratio-99.5% yield.
 Type and • Concentration of the catalyst

amount of • Homogeneous transesterification process unsuitable for

starting materials with high moisture and FFA content

catalyst • Yield esters increase with increasing amount of catalyst

• Oils and alcohols are not completely miscible

Mixing •
•
Reaction takes place only in the interfacial region
Intensity of mixing can be changed as per requirement
intensity • Effect of mixing becomes insignificant as phase
separation ends.

Free fatty • High FFA content more than 1% w/w, will lead to low
yield of biodiesel
acid and • Formation of gel and foams.
• Water content in WCO speeds up hydrolysis reaction
water content • Water content under 0.5% is desirable. 11
12
 GENERAL PROCESS OF PRODUCING BIODIESEL
PROCESS 1
• Filtration done to remove impurities from the WCO
• Feed stock preheated to 60℃
• Catalyst mixture and feedstock put into esterification reactor
• Operating Conditions- 80-90℃ and 1 atm. Pressure
• Mixture cooled, catalysts removed and bottom product is taken to process 2

PROCESS 2
• Catalyst mixture and products put into transesterification reactor
• Reaction Temperature- 65℃, 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 − 1 𝑎𝑡𝑚, Oil to methanol ratio- As required
• Products moved into the separator to separate biodiesel and methanol and water
• Biodiesel moved into the storage tank

PURIFICATION
• Done in a separating tank, either by settling or centrifuging
• Product is separated into 2-3 layers, top layer is biodiesel.
13
• Separation based on difference in densities.
• Biodiesel further washed with hot water to remove impurities and moisture.
PROCESS FLOWCHARTS

14
 A LOOK INTO A SOME OF THE
PROCESSES…
1.Biodiesel production by transesterification from WCO
by Zinc Stearate
• The zinc stearate immobilized on silica gel(ZS/Si) was the most effective catalyst in simultaneously
catalysing the transesterification of triglycerides and esterification of free fatty acid (FFA) present in
WCO to methyl esters.

• Zinc Stearate supported on silica gel was prepared using sol – gel method. The simultaneous
transesterification and esterification of WCO containing 15 wt.% free fatty acids was carried out using
prepared solid acid catalysts in a 500 cc Parr reactor.
• Pure zinc stearate - homogenous Lewis acid catalyst and one of its major drawbacks is the difficulty to
separate it from reaction products and to reuse. The TG analysis showed that the thermal stability of
supported zinc complex is higher than those of the pure zinc complex.
• The primary requirement of an ideal solid acid catalyst for biodiesel synthesis is large
interconnected pores that would minimize diffusional limitations of molecules having long alkyl
chains. The average pore diameter was 88 A.

• The catalyst recycling is an important step as it reduces the cost of the process. There was no loss in
the activity detected even after four recycles demonstrating the efficiency of the catalyst. Also,
negligible leaching or dissolution of zinc into the liquid portion was detected by ICP-MS analysis.

15
 2. Biodiesel production from
WCO using zeolites as catalyst
BIODIESEL
CHARACTERIZATION
CATALYST
REUSABILITY: - • The physical and
REACTION: - chemical properties of
• Reusability of zeolite PARAMETERS the biodiesel were
STARTING Carried out in catalysts was assessed in INVESTIGATED:-
five transesterification determined and
MATERIALS: - CATALYST: - transesterification Time, temperature, compared with petrol
cycles
WCO, reactor with catalyst diesel
Zeolites mixed with • After deactivation, the
methanol(99.9% magnetic stirring concentration,
KOH solution to raise zeolites can be • Density, kinematic
pure),KOH, natural and dispersed regenerated by methanol amount, viscosity, acid number,
activity.
zeolites(85% pure) catalyst. impregnation in 5 molar
mixing intensity, cetane index, flash,
Separation carried KOH solutions, again.
and water content cloud and pour points
out subsequently. within ASTM 16 ranges.
• Yield- 95-96%
 CONCLUSION AND FUTURE PROSPECTS
•Conventional sources of energy are constrained and on the verge of
depletion.
•Alternate sources of energy(nuclear,hydro) are costly and difficult to
harness.
•Biodiesel- low cost alternative with excellent fuel properties.
• Large scale use of WCOs will be economical and reduce disposal
problems
•Blends of biodiesel and petrol have fulfilled substituent fuel criteria
• Reusability of catalyst is the most important property which can make
them economical for industrial production.
•Use of enzyme catalysts encouraged to make the process more
environment friendly.
• R&D in this sphere has now gained serious space.
•Energy scenario in India can change for the good with the increase in
production of biodiesel.
•However, many obstacles must be considered, including the absence of a
systematic method of collecting WCOs from households, restaurants,
hotels and the food industry. More than 80 % of WCO is produced by
households. This is a huge amount in utilizing WCO as a raw material in
the production of biodiesel through transesterification.
17
BIBLIOGRAPHY
• http://www.arpnjournals.org/jeas/research_papers/rp_2016/jeas_0116_3357.pdf

• https://en.wikipedia.org/wiki/Biodiesel

• http://www.oilgae.com/ref/glos/transesterification.html

• https://en.wikipedia.org/wiki/Catalysis

• https://www.researchgate.net/publication/282712231_Review_of_the_Production_of_Biodiesel_from_Waste_Coo
king_Oil_using_Solid_Catalysts

• https://www.ripublication.com/ijpst17/ijpstv11n1_02.pdf

• https://www.academia.edu/1592274/Solid_acid_catalyzed_biodiesel_production_from_waste_cooking_oil

• Conversion of Waste Cooking Oil to Biodiesel ,Rummi Devi Saini Chemistry Department, SMDRSD College
Pathankot, 145001, India.

• VOL. 11, NO. 1, JANUARY 2016, ISSN 1819-6608 ARPN Journal of Engineering and Applied Sciences ©2006-2016
Asian Research Publishing Network (ARPN). All rights reserved. ,www.arpnjournals.com

• OVERVIEW OF CATALYSTS IN BIODIESEL PRODUCTION ,Nur Syakirah Talha and Sarina Sulaiman Department18
of Biotechnology Engineering, International Islamic University Malaysia, Kuala Lumpur, Malaysia
19